CN104169041A - Lead-free solder compositions - Google Patents
Lead-free solder compositions Download PDFInfo
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- CN104169041A CN104169041A CN201280039969.9A CN201280039969A CN104169041A CN 104169041 A CN104169041 A CN 104169041A CN 201280039969 A CN201280039969 A CN 201280039969A CN 104169041 A CN104169041 A CN 104169041A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/282—Zn as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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- Organic Chemistry (AREA)
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
A solder may include zinc, aluminum, magnesium and gallium. The zinc may be present in an amount from about 82% to 96% by weight of the solder. The aluminum may be present in an amount from about 3% to about 15% by weight of the solder. The magnesium may be present in an amount from about 0.5% to about 1.5% by weight of the solder. The gallium may be present in an amount between about 0.5% to about 1.5% by weight of the solder.
Description
the cross reference of related application
The application has required the priority of the provisional application that application number that on August 17th, 2011 submits is 61/524,610, and it is all incorporated herein for reference.
Technical field
Present disclosure relates to solder material and more specifically relates to nothing or substantially unleaded solder material.
Background technology
Solder material is for manufacture and the assembling of various electromechanics and electronic device.In the past, solder material comprises quite a large amount of lead conventionally to provide solder material required performance, for example fusing point, wettability, ductility and thermal conductivity.Some scolders based on tin are developed equally.In recent years, attempted production the unleaded of desired properties and Wuxi solder material are provided.
general introduction
In certain embodiments, solder composition can comprise the magnesium of the zinc of about 82-96 % by weight, the aluminium of about 3-approximately 15 % by weight, about 0.5-approximately 1.5 % by weight and the gallium of about 0.5-approximately 1.5 % by weight.In certain embodiments, solder composition can comprise the magnesium of about 0.75-approximately 1.25 % by weight and the gallium of about 0.75-approximately 1.25 % by weight.In other embodiments, solder composition can comprise approximately 1.0 % by weight magnesium and approximately 1.0 % by weight galliums.In embodiment further, solder composition can comprise the gallium of the zinc of about 82-96 % by weight, the aluminium of about 3-approximately 15 % by weight, the magnesium of about 0.5-approximately 1.5 % by weight, about 0.5-approximately 1.5 % by weight and the tin of about 0.1-approximately 2.0 % by weight.
Solder composition can comprise adulterant.In certain embodiments, solder composition comprises approximately 0.5 % by weight or adulterant still less.In other embodiments, adulterant comprises indium, phosphorus, germanium, copper or its combination.
In certain embodiments, solder composition can be unleaded.In other embodiments, solder composition can be Wuxi.
In certain embodiments, solder composition can be welding rod.In other other embodiment, it is to be less than the welding rod of approximately 1 millimeter that composition can be diameter.
In other embodiment of present disclosure, provide the method for the scolder that forms phosphorus doping.The method can be included under the normal pressure of inert gas and produce melt, and is billet (billet) by melt forming.This melt can comprise the phosphorus that solder material and amount are the about 5000ppm of about 10ppm-.In certain embodiments, solder material comprises at least one and is selected from the component of zinc, aluminium, bismuth, tin, copper and indium.In other other embodiment, the method is included in to produce with forming and between step, makes the additional step of inert gas through melt bubbling.
Although disclose multiple embodiments, by the detailed description that shows below and recorded illustrative embodiment of the present invention, other embodiments in addition of the present invention become apparent for those skilled in the art.Therefore, describe in detail and be considered in fact illustrative and nonrestrictive.
Brief description of the drawings
Fig. 1 shows the experimental facilities for the test of high angle outage.
Fig. 2 shows the experimental facilities for the test of low angle outage.
Fig. 3 shows the heat analysis of sample 34 in embodiment 2.
Fig. 4 shows the heat analysis of sample 35 in embodiment 2.
describe in detail
Solder composition is in conjunction with two base materials or workpiece and have melting metal and the metal alloy of the fusing point lower than workpiece.Solder composition, for example, connect those of application for semiconductor industry chips (die), can many multi-form providing, include but not limited to bulk (bulk) scolder product, soldering paste and welding rod.
Soldering paste can be fluid or putty-like material, and it can make in all sorts of ways and be applied to base material, includes but not limited to printing and distributes, for example, use syringe.Exemplary paste composition can be by making brazing metal and the solder flux (flux) of powder, and dense thick (thick) medium that serves as temporary adhesive mixes and forms.This solder flux can make soldering paste component keep together until scolder technique melting powder scolder.According to how soldering paste being applied to base material, the appropriate viscosity of soldering paste may be different.The appropriate viscosity of soldering paste comprises 300,000-700,000 centipoise (cps).
In other embodiments, solder composition can be used as welding rod provides.Welding rod can be by drawing solder material to provide thin welding rod to form on bobbin via mouth mould (die).Suitable welding rod can have the diameter that is less than approximately 1 millimeter (mm), for example the about 0.8mm of about 0.3-.In certain embodiments, can be wound around or to be coiled on bobbin and not break be two sections or multistage more to welding rod.For example, can be wrapped in inner shaft diameter be on 51mm and two the external flange diameters bobbin that is 102mm to welding rod.Along with welding rod is wrapped on bobbin, the part welding rod of close inner shaft is wound in the bobbin that effective diameter is about 51mm.Along with other welding rod is wrapped on bobbin, the effective diameter of bobbin increases because of welding rod, and on inner shaft, forms after multiple electrode rings, and the effective diameter of bobbin can be and more approaches 102mm than 51mm.
Do not consider form, solder composition can be evaluated its solidus (solidus) temperature, melt temperature scope, wettability, ductility and thermal conductivity.Temperature when solidus temperature starts melting with solder material quantizes.Lower than solidus temperature, solder material is completely curing.In certain embodiments, solidus temperature can be 300 DEG C of left and right to allow classification welding (step soldering) operation and the thermal stress in final use equipment to be down to minimum.
The melt temperature scope of solder composition is by solidus temperature and liquidus temperature definition.The temperature of liquidus temperature during with the complete melting of solder material quantizes.Liquidus temperature for crystal (for example solid material) wherein can with the simultaneous maximum temperature of melt (for example fluent material).During higher than liquidus temperature, solder material is homogeneous phase melt or liquid.In certain embodiments, can preferably have and make the scope that scolder exists in two-phase be down to minimum narrow melt temperature scope.
Wetability refers to flow of solder material and makes base material or ability that surface of the work is moistening.The wetability improving provides the adhesion strength of the increase between workpiece conventionally.Can use a wet test (dot wet test) to measure wetability.
All welding points strength of welded joint that experience reduces within equipment life in terminal device.There is the scolder of ductility of raising by the extension device life-span and more cater to the need.Ductile scolder also more conforms with and can make welding rod can coil or be wrapped in the needs on bobbin in the manufacture of below recording.Available line bending shaft testing machine is measured ductility and can be comprised low angle (being less than 90 °) and the measurement of high angle (being greater than 90 °) ductility.Suitable ductility value depends on the final use of solder material.In certain embodiments, suitable solder material can have 0% high angle outage and be less than 50%, is less than 40% or be less than 30% low angle outage.
High heat conductance may be also that equipment performance is required.In certain embodiments, solder material can make chip be connected to lead frame.In this embodiment, it may be desirable for scolder, heat conduction being entered to lead frame.In some instances, high heat conductance for high power applications for desirable especially.In certain embodiments, suitable solder material can have the thermal conductivity that is greater than 20 watts of every meter of Kelvins (W/m-K).The thermal conductivity of in other embodiments, suitable solder material can be and is greater than 10W/m-K or from 10W/m-K to about W/m-K.In other embodiments, the thermal conductivity of solder material is low to moderate 10,12,14W/m-K or high to 15,18,20 or 25W/m-K or can be in any scope being limited by arbitrary right above-mentioned value.
Solder material can be unleaded.For example can be unleaded based on solder material zinc/aluminium or based on bismuth/copper." unleaded " used herein refers to that solder material comprises the lead that is less than 0.1 % by weight.In certain embodiments, solder material can be Wuxi.For example can be Wuxi based on solder material zinc/aluminium or based on bismuth/copper." Wuxi " used herein refers to that solder material comprises the tin that is less than 0.l % by weight.
In certain embodiments, the solder material based on zinc/aluminium can comprise zinc and aluminium as key component and magnesium and gallium as accessory constituent.In certain embodiments, the solder material based on zinc/aluminium can comprise the magnesium of the zinc of about 82-approximately 96 % by weight, the aluminium of about 3-approximately 15 % by weight, about 0.5-approximately 1.5 % by weight and the gallium of about 0.5-approximately 1.5 % by weight.In specific embodiment, zinc can be low to moderate 82,84 or 86 % by weight or the high amount to 92,94 or 96 % by weight exists, or exist in any scope can a pair of above-mentioned numerical value in office limiting; Aluminium can be low to moderate 2,3,4 % by weight, or the high amount to 5,7,10,12 or 15 % by weight exists, or exists in any scope can a pair of above-mentioned numerical value in office limiting; Magnesium can be low to moderate 0.5,0.75 or 0.9 % by weight, or the high amount to 1.0,1.25 or 1.5 % by weight exists, or exists in any scope can a pair of above-mentioned numerical value in office limiting; And gallium can be low to moderate 0.5,0.75 or 0.9 % by weight, or the high amount to 1.0,1.25 or 1.5 % by weight exists, or exists in any scope can a pair of above-mentioned numerical value in office limiting.In other other embodiment, the solder material based on zinc/aluminium can comprise aluminium, the magnesium of approximately 1.0 % by weight and the gallium of approximately 1.0 % by weight of the zinc of about 82-approximately 96 % by weight, about 3-approximately 15 % by weight.
In certain embodiments, for example indium, phosphorus, germanium, tin and/or copper of adulterant can the amount with the about 5000ppm of about 10-(or about 0.001-approximately 0.5 % by weight) exist in solder material.In other embodiments, for example indium, phosphorus, germanium, tin and/or copper of adulterant can exist with the amount of about 0.001-approximately 2.5 % by weight in solder material.In certain embodiments, the amount of the phosphorus comprising in solder material can be low to moderate 10ppm, 25ppm, 50ppm or 100ppm or high to 150ppm, 300ppm, 500pm, 1000ppm or 5000ppm, or exists in any scope can a pair of above-mentioned numerical value in office limiting; In other embodiments, the amount of the tin comprising in solder material can be low to moderate 0.1,0.25,0.5 or 0.75 % by weight or high to 1.0,1.25,1.5,1.75 or 2.0 % by weight, or exists in any scope can a pair of above-mentioned numerical value in office limiting; In other other embodiment, the amount of the copper comprising in solder material can be low to moderate 0.1,0.25,0.5 or 0.75 or high to 1.0,1.25,1.5,1.75 or 2.0 % by weight, or exists in any scope can a pair of above-mentioned numerical value in office limiting.
Scolder can comprise independent a kind of dopant material, maybe can comprise the combination of two or more dopant materials.In certain embodiments, solder composition can comprise phosphorus and tin as dopant material.For example, solder composition can comprise and is low to moderate 10ppm, 25ppm, 50ppm or 100ppm or high to 150ppm, 300ppm, 500pm, 1000ppm or 5000ppm, or the phosphorus of the amount existing in any scope can a pair of above-mentioned numerical value in office limiting; And tin can be low to moderate 0.1,0.25,0.5 or 0.75 % by weight or high to 1.0,1.25,1.5,1.75 or 2.0 % by weight, or amount in any scope can a pair of above-mentioned numerical value in office limiting exists; In other embodiments, solder composition can comprise phosphorus and copper as dopant material.For example, solder composition can comprise and is low to moderate 25ppm, 50ppm or 100ppm or high to 150ppm, 300ppm, 500pm, 1000ppm or 5000ppm, or the phosphorus of the amount existing in any scope can a pair of above-mentioned numerical value in office limiting; With can be low to moderate 0.1,0.25,0.5 or 0.75 or high to 1.0,1.25,1.5,1.75 or 2.0 % by weight, or the copper of the amount existing in any scope can a pair of above-mentioned numerical value in office limiting.
In certain embodiments, the solder material based on zinc/aluminium can by or substantially formed by the magnesium of the aluminium of approximately 12 % by weight, approximately 1 % by weight, gallium, approximately 0.5 adulterant of % by weight and the zinc of surplus of approximately 1 % by weight.Adulterant can be listed the single of those above and plants material or can be its combination.
In other embodiments, the solder material based on zinc/aluminium can be made up of the magnesium of the aluminium of approximately 5 % by weight, approximately 1 % by weight, approximately 1 gallium of % by weight and the zinc of surplus.In other other embodiment, the solder material based on zinc/aluminium can be made up of the phosphorus of the gallium of the magnesium of the aluminium of about 2-approximately 15 % by weight, approximately 1 % by weight, approximately 1 % by weight, 50-150ppm, about 0.5-approximately 1.5 tin of % by weight and the zinc of surplus.In other other embodiment, the solder material based on zinc/aluminium can be made up of the gallium of the magnesium of the aluminium of about 2-approximately 15 % by weight, approximately 1 % by weight, approximately 1 % by weight, the phosphorus of the about 150ppm of about 50ppm to, about 0.2-approximately 0.6 copper of % by weight and the zinc of surplus.
In certain embodiments, the solder material based on zinc/aluminium can comprise zinc and aluminium as major part and germanium as accessory constituent.In certain embodiments, the solder material based on zinc/aluminium can comprise the aluminium of the zinc of about 78-approximately 94 % by weight, about 3-approximately 15 % by weight and the germanium of about 3-approximately 7 % by weight.If comprised, the amount that adulterant for example indium, phosphorus, gallium and/or copper can the about 5000ppm of about 0-(or about 0-approximately 0.5 % by weight) exists.Solder composition can comprise independent a kind of dopant material, maybe can comprise the combination of two or more dopant materials.
In one embodiment, the solder material based on zinc/aluminium can comprise gallium, approximately 0.1 adulterant of % by weight and the zinc of surplus of the aluminium of approximately 6 % by weight, approximately 5 % by weight.Adulterant can be listed the single of those above and plants material or can be its combination.
In certain embodiments, the solder material based on bismuth/copper can comprise the bismuth of about 88-approximately 92 % by weight and the copper of about 8-approximately 12 % by weight.Adulterant for example gallium, indium, phosphorus and/or germanium can the about 1000ppm of about 10ppm-(or approximately 0.001 % by weight-Yue 0.1 % by weight) amount exist.Solder composition can comprise independent a kind of dopant material, maybe can comprise the combination of two or more dopant materials.
In certain embodiments, the solder material based on bismuth/copper can be made up of the copper of approximately 10 % by weight, approximately 0.1 adulterant of % by weight and the bismuth of surplus.Adulterant can be listed the single of those above and plants material or can be its combination.
Solder material based on bismuth/copper can show lower melt temperature and thermal conductivity, thereby can be suitable for low power applications, and shows higher melt temperature and thermal conductivity based on the solder material of zinc/aluminium, thereby can be suitable for high power applications.
May be difficult to form the homogeneous solder material that comprises phosphorus dopant.For example, may be difficult to during fabrication phosphorus and scolder melt mixed.In certain embodiments, the melt that solder material can comprise base solder material and phosphorus dopant by generation forms.In certain embodiments, the amount that phosphorus can the about 5000ppm of about 10ppm-exists.In other embodiments, base solder material can comprise following one or more: zinc, aluminium, bismuth, tin, copper and indium.In certain embodiments, can under normal pressure, heat base solder material and phosphorus dopant to form melt.For example, can be by inert gas, for example argon gas or nitrogen, under normal pressure, keep melt.Normal pressure can be avoided the evaporation loss of phosphorus dopant.
In addition, inert gas can be through melt bubbling to promote the mixing of base solder material and phosphorus and to form homogeneous melt.After mixing, melt can and be cast into billet by die extrusion.In certain embodiments, fusion welding can, being less than in 1 minute, be cured as solid-state in foundry goods.In other embodiments, fusion welding can be being less than 30 seconds, be less than 10 seconds or be less than in 5 seconds and solidify in foundry goods.The quick cooling separation that suppresses for example phosphorus of dopant material of billet, and can cause distributing along the Uniform Doped agent of billet.For example as-cast billet can be along axially having uniform dopant distribution.
embodiment 1-zinc/aluminium solder alloy
I. the formation of solder alloy billet
Zinc/aluminium solder alloy forms by the billet that zinc, aluminium, magnesium and gallium casting is become to 1 inch diameter in blanket of nitrogen.
With zinc/aluminium solder alloy of phosphorus and tin dope by adding tin/phosphate alloy preparation of phosphorus (Sn5P) of the tin that comprises 95 % by weight and 5 % by weight, and by zinc/aluminium solder alloy of preparation above to Rautomead conticaster.
Heating material to 450-550 DEG C with form melt.Melt is remained on to direct draught.Inert gas passes melt bubbling until obtain homogeneous melt.Via die extrusion melt and cast the billet of 1 inch diameter.
With zinc/aluminium solder alloy of phosphorus and copper doping by adding copper/phosphoric acid alloy preparation of phosphorus (Cu15P) of the copper that comprises 85 % by weight and 15 % by weight, and by zinc/aluminium solder alloy of preparation above to Rautomead conticaster.Form melt by making casting machine be increased to 800-900 DEG C.Melt is remained on to direct draught.Via die extrusion melt and cast the billet of 1 inch diameter.
The melt preparation of the zinc/aluminium solder alloy that comprises into above preparation by formation with zinc/aluminium solder alloy of indium doping and indium.Make melt cast the billet of 1 inch diameter.
II. test program
Under 200-300 DEG C and 1500-2000 pound/square inch (psi), by die extrusion solder alloy billet to form the welding rod of diameter as about 0.762mm (0.030 inch).It is that 51mm (2 inches) and two external flange diameters are on the bobbin of 102mm (4 inches) that welding rod is wrapped in inner shaft diameter.Can successfully the welding rod of extruding be wrapped on bobbin and not be broken into two sections or multistage more.
The melting characteristic of welding rod uses Perkin Elmer DSC7 machine to be measured by differential scanning calorimetry (" DSC ").Measure solidus temperature and liquidus temperature.Calculate poor as between liquidus temperature and solidus temperature of melt temperature scope.
The percentage elongation of welding rod is at room temperature according to the ASTM E8 that is called " Standard Test Methods for Tension Testing of Metallic Materials ", with the measurement of Instron4465 machine.
At room temperature measure low angle outage and the high angle outage of welding rod, to study the ductility of welding rod.For the test of each outage, the inner shaft that welding rod is wrapped in ceases to be busy axle around and after being recorded in that inner shaft is last and being wound around welding rod whether rupture.Repeatedly test and calculate the broken string percentage of each sample.
Fig. 1 has illustrated the experimental facilities for the test of high angle outage.
As shown, bobbin 10 comprises flange 12, inner shaft 14 and groove 16.Inner shaft 14, between parallel flanges 12, produces hole between them.The diameter of inner shaft 14 is 51mm, and the diameter of flange 12 is 102mm.Groove 16 is in the interior formation of inner shaft 14.One end insertion groove 16 and the welding rod 18 of welding rod 18 are wrapped on inner shaft 14.As shown in Figure 1, welding rod 18 ends in hole 16 be wrapped in the welding rod 18 angulation A in inner shaft 14.Angle A is greater than 90 °.Fig. 2 shows the experimental facilities of low angle outage test.Again, in one end insertion groove 16 of welding rod 18.In low angle bend test, welding rod 18 ends in groove 16 be wrapped in the welding rod 18 angulation B in inner shaft 14.Angle B is less than 90 °.
Use ASM SD890A die bonder to measure solder wetting with the formation gas (forming gas) that comprises 95 volume % nitrogen and 5 volume % hydrogen at 410 DEG C.Welding rod is fed to hot copper lead frame, make welding rod melting and form a little on lead frame.The size (for example diameter) of measurement point.The wetability of the corresponding welding rod of size of point, the better wetability of the larger correspondence of size of point.
III. result
Form the welding rod of 0.030 inch diameter and be wrapped on bobbin by die extrusion billet.Table 1 provides the composition of successfully extruding and form the welding rod of electrode ring on bobbin.The welding rod of table 2 causes fragility electrode ring maybe can not form electrode ring.
Table 1, be successfully extruded into the composition of welding rod and winding
Table 2, the unsuccessful composition of extruding and being wound around
As shown in Tables 1 and 2, in the time that gallium content is greater than 1.5 % by weight, forms fragility electrode ring, and cannot form electrode ring in the time that gallium content is greater than 1.7 % by weight.Especially, after final cold rod stretches, welding rod cannot successfully be wrapped on winding bobbin.Similarly, in the time that content of magnesium is greater than 1.5 % by weight, form fragility electrode ring.
In the time adulterating zinc/aluminium alloy with indium, cannot successfully form electrode ring (for example, referring to sample 30,31,32).
The melting characteristic of zinc/aluminium alloy electrode of extruding is presented in table 3.The melting characteristic of doping zinc/aluminium alloy electrode of extruding is presented in table 4.
The melting characteristic of table 3, zinc/aluminium alloy electrode
The melting characteristic of the zinc/aluminium alloy electrode of table 4, doping
As shown in table 3, along with gallium content raises, solidus temperature and liquidus temperature reduce conventionally.Similarly, along with content of magnesium raises, solidus temperature and liquidus temperature reduce conventionally.
Notice in the time that gallium content is less than 0.5 % by weight melting range narrower (comparing with 5 with sample 4 with 2 referring to sample 1).But the solidus temperature of sample 1 and 2 and liquidus temperature are higher than sample 4 and 5.
In the time that content of magnesium is less than 0.5 % by weight, melting range narrower equally (comparing with 6 with sample 14 with 12 referring to sample 11).The solidus temperature of sample 11 and 12 and liquidus curve be higher than sample 14 and 6, thereby need more substantial heat for solder sample 11 and 12.
As shown in table 4, reduce solidus temperature (for example sample 5 and sample 24 relatively) with tin/phosphorus doping.Solidus temperature or liquidus temperature are seemed not have remarkable impact (for example sample 27 and sample 5 are relatively) with copper/phosphorus doping.
The mechanical performance of zinc/aluminium alloy electrode of extruding is presented in table 5.The mechanical performance of doping zinc/aluminium alloy electrode of extruding is presented in table 6.
The mechanical performance of table 5, zinc/aluminium alloy electrode
The mechanical performance of the zinc/aluminium alloy electrode of table 6, doping
As shown in table 5, comprise the percentage elongation higher than the solder material of 1.0 % by weight galliums with obvious reduction.Comprise lower than the solder material of 0.5 % by weight gallium and there is relatively low percentage elongation (being for example less than 7% percentage elongation).Comprise the percentage elongation higher than the solder material of 1.0 % by weight magnesium with obvious reduction, below
As shown in table 6, reduce the percentage elongation (for example, comparative sample 24 and sample 5 and sample 27 and sample 5) of solder material adding of tin/phosphorus or copper/phosphorus dopant.The percentage elongation of sample 26 is not determined.
In certain embodiments, the high angle outage (Bend BR-HA) that there is the welding rod of acceptable ductility be 0% and low angle outage (Bend BR-LA) for being less than 30%.The welding rod ductility result of gratifying welding rod is presented in table 7.The sample welding rod that does not meet required high angle and low angle outage is presented in table 8.
Table 7, there is the welding rod of gratifying outage
| Sample | Bend?BR-HA | Bend?BR-LA |
| 1 | 0％ | 0％ |
| 2 | 0％ | 0％ |
| 3 | 0％ | 0％ |
| 4 | 0％ | 0％ |
| 5 | 0％ | 0％ |
| 11 | 0％ | 0％ |
| 12 | 0％ | 0％ |
| 13 | 0％ | 0％ |
| 14 | 0％ | 0％ |
| 24 | 0％ | 0％ |
| Sample | Bend?BR-HA | Bend?BR-LA |
| 25 | 0％ | 20％ |
| 28 | 0％ | 20％ |
Table 8, there is the welding rod of not satisfied outage
| Sample | Bend?BR-HA | Bend?BR-LA |
| 6 | 0％ | 40％ |
| 7 | 0％ | 100％ |
| 8 | 0％ | 100％ |
| 9 | 20％ | 100％ |
| 10 | 40％ | 100％ |
| 15 | 0％ | 80％ |
| 16 | 0％ | 100％ |
| 17 | 0％ | 100％ |
| 18 | 0％ | 100％ |
| 19 | 0％ | 100％ |
| 20 | 100％ | 100％ |
| 21 | 100％ | 100％ |
| 22 | 100％ | 100％ |
| 23 | 100％ | 100％ |
| 26 | 100％ | 100％ |
| 27 | 0％ | 50％ |
| 29 | 0％ | 40％ |
As shown in table 6 and 7, in the time that gallium content is greater than 1.0 % by weight, low angle outage is for being greater than 30%.Similarly, in the time that content of magnesium is greater than 1.0 % by weight, low angle outage is for being greater than 30%.
Solder wetting is presented in table 9, and wherein larger wet point size shows the wettability strengthening.
The solder wetting of the zinc/aluminium welding wire of table 9, zinc/aluminium and doping
Do not test sample 9,10,19,20,21,22,23 and 26.As shown in table 9, add gallium approximately 0.75 % by weight raising wettability extremely at the most, in wetability reduction thereafter.In addition, add magnesium conventionally to improve wetability.
Add tin/phosphorus dopant to reduce wetability slightly and add copper/phosphorus dopant to improve wetability.
the contrast of embodiment 2-solder material
I. the formation of welding rod
By produce following expression each component melt, to cast billet and form diameter by die extrusion billet be that the welding rod of 0.762mm (0.030 inch) forms kupper solder, bismuth solder and zinc-aluminium scolder.
Sample 33:92.5 % by weight lead, 5 % by weight indiums, 2.5 % by weight silver
Sample 34:89.9 % by weight bismuth, 10 % by weight copper, 0.1 % by weight gallium
Sample 35:93.5 % by weight zinc, 4.5 % by weight aluminium, 1 % by weight magnesium, 1 % by weight gallium
II. test program
Mensuration solidus temperature and percentage elongation as described in Example 1.
The thermodynamic analysis of solder composition uses Perkin Elmer DSC7 machine to measure by differential scanning calorimetry (" DSC ").
The sample diffusion of solder material is used Nanoflash machine to measure.The thermal conductivity of each solder material is used diffuseness values to calculate.
Calculate the thermal coefficient of expansion (CTE) of each scolder.The sample length of each material changes with the measurement of thermo-mechanical analysis device and calculates to measure CTE with respect to temperature.
Under given voltage, measure the resistance of solder material by using Electrical Measuring Instrument to measure sample resistance with given length range.Use the long-pending calculated resistance rate of resistance and example cross section.
On the ASM die bonder Lotus-SD with scolder writing ability, carry out chips welding test with model chip (dummy die).Lead frame uses the copper of ASM inhouse TO220 naked copper and nickel plating.Model chip is of a size of 2x3mm, with titanium, nickel, silver (Ti/Ni/Ag) back face metalization.The formation gas that comprises 95 volume % nitrogen and 5 volume % hydrogen in order to lower area setup and use: 5 liters/min of kinds (LPM) preheat district (preheat zone) 1,5LPM and preheat that district 2,5LPM preheat district 3,2LMP distributes district (dispense zone), 2LPM to bounce district (spank zone), 2LPM weld zone (bond zone) and 2LMP cooling zone (cooling zone).The weld zone time is 700 milliseconds, and it is 2,200 microns that scolder distributes speed, has 9-straight line " z " pattern.Regional temperature is set different.
Measuring chip with chip shearing test device shears.Promote chip along mouth mould edge until chip splits or base material is sheared.Record shearing force by chip shearing test device.
By four angular measurement chips inclinations (die tilt) of the welding chip with micrometer measurement.Tilt as the maximum differential computing chip between reading.
Measure weld zone (bond line) by measure chip thickness, welding chip thickness and base material thickness with micrometer.The thick through type in weld zone (1) calculates.
Weld zone is thick=welding chip thickness-chip thickness-base material thickness (1)
III. result
The physical condition of solder material is presented in table 10.
Table 10, scolder physical property
The solidus temperature of bismuth solder (sample 34) and thermal conductivity (thermal conductivity, theme cond) lower than kupper solder (sample 33), advise that bismuth solder should be used for limited rear chip and connect thermal process and/or the low-power equipment application to high heat conductance no requirement (NR).
Spelter solder (sample 35) has higher solidus temperature and thermal conductivity than kupper solder (sample 33), makes spelter solder can be used for high power and high temperature application.Compared with kupper solder (sample 33), bismuth solder (sample 34) and the low elongation of spelter solder (sample 35) make scolder more not flexible to absorb after being connected at chip and to alleviate thermal stress.
The heat analysis of sample 34 and 35 is presented on respectively in Fig. 3 and 4.As shown in Figure 3, the solidus temperature of sample 34 is 271 DEG C.
Because not melting of copper is until it reaches temperature higher than 700 DEG C, it is composite alloy that alloy connects at temperature at the chip of 360-400 DEG C.The bismuth that the melting of sample 34 can be mainly passed through in wetting and welding ensures.In addition, micron-scale copper particle can contribute to controlling sprawl and can the provide equipment of molten bismuth on base material during chip connects and prepare rear required thermal conductivity at chip connection temperature.
As shown in Figure 4, sample 35 has the solidus temperature of 337 DEG C.Be solid reaction at the low temperature peak of 272 DEG C and do not affect melt solder characteristic.
Carry out chips welding test and the temperature in each region is adjusted to realization moistening, chips welding uniformly.Process conditions and result are presented in table 11, and wherein LF represents lead frame, and PH1 is the temperature that preheats region 1, and PH2/3 is that the temperature, the D/S/B that preheat region 2 and 3 distributes, bounces and the temperature of welding region, and the Cool temperature that is cooling zone.
Table 11, chip connect process conditions
Chips welding sample is sheared for test chip.Result is presented in table 12.
Table 12, chip are sheared result
All samples show enough shearing forces and cohesion failure pattern.
Chips welding sample be used for testing tilt and weld zone thick.Result is presented in table 13.
Table 13, chip tilt and the thick result in weld zone
All samples shown be connected with common chip application in suitable numerical value.
Can carry out various improvement and increase to the exemplary embodiment of discussing, and not depart from the scope of the present invention.For example, in the time that embodiment as above relates to specific feature, scope of the present invention also comprises the embodiment with different characteristic combination and the characteristic embodiment that does not comprise above record.
Claims (20)
1. a solder composition, comprises:
The zinc of about 82-96 % by weight;
The aluminium of about 3-approximately 15 % by weight;
The magnesium of about 0.5-approximately 1.5 % by weight; With
The gallium of about 0.5-approximately 1.5 % by weight.
2. according to the solder composition of claim 1, comprise:
The magnesium of about 0.75-approximately 1.25 % by weight; With
The gallium of about 0.75-approximately 1.25 % by weight.
3. according to the solder composition of claim 1, comprise:
The magnesium of approximately 1.0 % by weight; With
The gallium of approximately 1.0 % by weight.
4. according to the solder composition of claim 1, and further comprise:
The tin of about 0.1-approximately 2.0 % by weight.
5. according to the solder composition of claim 1, and further comprise the adulterant that at least one exists with the amount of about 0.001-approximately 0.5 % by weight.
6. according to the solder composition of claim 5, wherein at least one adulterant comprises one or more in indium, phosphorus, germanium or copper.
7. according to the solder composition of claim 5, wherein adulterant comprise phosphorus and be selected from germanium and the group of copper composition at least one.
8. according to the solder composition of claim 1, and further comprise:
The phosphorus of the about 1000ppm of about 10ppm-; With
The tin of about 0.1-approximately 2 % by weight.
9. according to the solder composition of claim 1, and further comprise:
The phosphorus of the about 300ppm of about 25ppm-; With
The tin of about 0.5-approximately 1.5 % by weight.
10. according to the solder composition of claim 1, and further comprise:
The phosphorus of the about 300ppm of about 25ppm-; With
The copper of about 0.1-approximately 1 % by weight.
11. according to the solder composition of claim 1, and further comprises:
Be less than the lead of approximately 0.1 % by weight.
12. according to the solder composition of claim 1, and further comprises:
Be less than the tin of approximately 0.1 % by weight.
13. according to the solder composition of claim 1, and wherein this solder composition is made up of zinc, aluminium, gallium and magnesium.
14. according to the solder composition of claim 1, and wherein this solder composition is made up of zinc, aluminium, gallium, magnesium, tin and phosphorus.
15. according to the solder composition of claim 1, and wherein this solder composition is made up of zinc, aluminium, gallium, magnesium and at least one adulterant.
16. according to the solder composition of claim 1, and wherein this solder composition is welding rod.
17. according to the solder composition of claim 16, and wherein the diameter of this welding rod is less than approximately 1 millimeter.
18. 1 kinds form the method for the scolder of phosphorus doping, and the method comprises:
Under the normal pressure with inert gas, produce melt; And
Be billet by melt forming, wherein this melt comprises the phosphorus that solder material and amount are the about 5000ppm of about 10ppm-.
19. according to the method for claim 18, and wherein this solder material comprises at least one and be selected from the component of the group of zinc, aluminium, bismuth, tin, copper and indium composition.
20. according to the method for claim 18, further comprises, is producing and is forming between step, makes the additional step of inert gas through melt bubbling.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161524610P | 2011-08-17 | 2011-08-17 | |
| US61/524,610 | 2011-08-17 | ||
| US13/586,074 US20130045131A1 (en) | 2011-08-17 | 2012-08-15 | Lead-Free Solder Compositions |
| US13/586,074 | 2012-08-15 | ||
| PCT/US2012/051343 WO2013025990A2 (en) | 2011-08-17 | 2012-08-17 | Lead-free solder compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104169041A true CN104169041A (en) | 2014-11-26 |
Family
ID=47712785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280039969.9A Pending CN104169041A (en) | 2011-08-17 | 2012-08-17 | Lead-free solder compositions |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20130045131A1 (en) |
| KR (1) | KR20140050728A (en) |
| CN (1) | CN104169041A (en) |
| TW (1) | TW201313376A (en) |
| WO (1) | WO2013025990A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10046417B2 (en) | 2011-08-17 | 2018-08-14 | Honeywell International Inc. | Lead-free solder compositions |
| CN111168273A (en) * | 2020-02-12 | 2020-05-19 | 郑州大学 | Flux-cored welding rod for stainless steel welding |
| CN111250896A (en) * | 2020-03-26 | 2020-06-09 | 郑州机械研究所有限公司 | High-strength, corrosion-resistant and low-melting brazing filler metal for aluminum alloy honeycomb plate and preparation method |
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| JP2014151364A (en) * | 2013-02-13 | 2014-08-25 | Toyota Industries Corp | Solder and die bond structure |
| US9520347B2 (en) | 2013-05-03 | 2016-12-13 | Honeywell International Inc. | Lead frame construct for lead-free solder connections |
| US20150151387A1 (en) | 2013-12-04 | 2015-06-04 | Honeywell International Inc. | Zinc-based lead-free solder compositions |
| TWI561639B (en) | 2014-04-17 | 2016-12-11 | Heraeus Materials Singapore Pte Ltd | Lead-free eutectic solder alloy comprising zinc as the main component and aluminum as an alloying metal |
| HUE045443T2 (en) * | 2014-08-27 | 2019-12-30 | Heraeus Deutschland Gmbh & Co Kg | Soldering paste and process of cohesive connection |
| CN106660176B (en) * | 2014-08-27 | 2020-11-10 | 贺利氏德国有限两合公司 | Method for producing a welded joint |
| JP2019107700A (en) * | 2019-02-18 | 2019-07-04 | ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． | Lead-free solder composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20140050728A (en) | 2014-04-29 |
| TW201313376A (en) | 2013-04-01 |
| US20150004427A1 (en) | 2015-01-01 |
| WO2013025990A3 (en) | 2013-04-25 |
| WO2013025990A2 (en) | 2013-02-21 |
| US20130045131A1 (en) | 2013-02-21 |
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